Water borne film-forming compositions

ABSTRACT

The present invention provides a film-forming composition comprising a particulate polymer or emulsified liquid pre-polymer, water and a coalescent aid comprising an ester having the formula RCOOX wherein R and X are independently hydrocarbyl or substituted hydrocarbyl, and at least one of R and X contain at least two unsaturated carbon-carbon bonds. The coalescent aid helps lower the minimum film formation temperature of low glass transition temperature coatings and high glass transition temperature coatings and allows optimum film formation at ambient temperatures. The coalescent aid of this coating composition is not volatile like conventional coalescent aids but rather remains part of the film and air oxidizes to cure the film. This coating composition also exhibits properties of adhesion and gloss superior to that of coating compositions containing conventional coalescent aids. Additionally, this coalescent aid can be made from natural or synthetic oils.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 10/643,612,filed Aug. 19, 2003, which is a continuation of application Ser. No.09/532,839, filed Mar. 21, 2000, which claims priority from applicationSer. No. 60/125,446, filed Mar. 22, 1999, the contents of which arehereby incorporated by reference in their entirety.

FIELD OF THE INVENTION

This invention generally relates to water borne film-formingcompositions containing a polyunsaturated ester as a coalescent aid.

BACKGROUND OF THE INVENTION

Aqueous dispersions of particulate polymer or emulsified liquidpre-polymers for use as paints, sealants, caulks, adhesives or othercoatings are well-known, widely-used articles of commerce. Theeffectiveness of the dispersion in forming a film after the polymerdispersion has been deposited upon a surface depends upon the glasstransition temperature of the dispersed polymer and the temperature atwhich the film is allowed to dry. See, for example, Conn et al., U.S.Pat. No. 2,795,564 and Emmons et al., U.S. Pat. No. 4,131,580.

Coalescent aids have been used in such aqueous dispersions to soften,i.e., plasticize, the particulate polymers and facilitate the formationof a continuous film with optimum film properties once the water hasevaporated. In addition to increasing the ease of film formation, thecoalescent aid also promotes subsequent improvements in film propertiesby coalescing the particulate polymers and liquid pre-polymers andforming an integral film at ambient temperatures. Without the coalescentaid, the films may crack and fail to adhere to the substrate surfacewhen dry.

Coalescent aids are particularly helpful in assisting the formation ofparticulate polymer films possessing a high glass transitiontemperature, that is, the temperature which defines how easily theparticles of the polymer diffuse at the temperature at which thefilm-forming composition is applied. The presence of coalescent aids ina particulate polymer film having a high glass transition temperatureallows optimum film formation at ambient temperatures.

Various alcohol esters and ether alcohols have been proposed for use ascoalescent aids. For example, in U.S. Pat. No. 4,131,580 Emmons et al.disclose water-based coating compositions based on vinyl additionpolymers of monoethylenically unsaturated monomers which comprisedicyclopentenyl acrylate and/or dicyclopentenyl methacrylate as acoalescent aid. In U.S. Pat. No. 4,141,868, Emmons et al. suggestcertain ester-ether compounds be used instead. Two of the more widelyused coalescent aids are ethylene glycol monobutyl ether (EB, UnionCarbide) and 2,2,4-trimethyl-1,3 pentanediol monobutyrate (TEXANOL®,Eastman Kodak). While EB and TEXANOL® are useful in facilitating filmformation of particulate polymer coatings with high glass transitiontemperatures and are even useful in facilitating film formation ofparticulate polymer coatings with low glass transition temperatures ifthey are being applied at a temperature that is lower than ambienttemperature, they are relatively volatile and, as a result, arecurrently classified as VOCs (volatile organic compounds).

SUMMARY OF THE INVENTION

Among the objects of the invention is a coalescent aid for use in awater-borne film forming composition wherein the coalescent aid is notclassified as a volatile organic compound, but which, nevertheless, (i)exhibits favorable adhesion and gloss relative to water bornefilm-forming compositions containing conventional coalescent aids, (ii)exhibits favorable minimum film formation temperature of low glasstransition temperature films and high glass transition temperature filmsand (iii) allows optimum film formation at ambient temperatures.

Briefly, therefore, the present invention provides a film-formingcomposition comprising a continuous aqueous phase and a dispersed phase.The dispersed phase comprises (i) a particulate polymer or emulsifiedliquid prepolymer, and (ii) a coalescent aid comprising an ester havingthe formula RCOOX wherein R and X are independently hydrocarbyl orsubstituted hydrocarbyl and at least one of R and X comprises at leasttwo unsaturated carbon-carbon bonds. Other objects of the invention willbe in part apparent and in part pointed out hereinafter.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the MFFT (C) plot for FLEXBOND 325 as a function of %coalescent aids;

FIG. 2 is the MFFT (C) plot for UCAR 379 as a function of % coalescentaids;

FIG. 3 is the MFFT (C) plot for ACRONAL A846 as a function of %coalescent aids;

FIG. 4 is the MFFT (C) plot for UCAR 430 as a function of % coalescentaids;

FIG. 6 is the MFFT plot for UCAR 430 as a function of coalescent aids;

FIG. 7 is the MFFT plot for UCAR 430 as a function of coalescent aids;

FIG. 8 is the MFFT plot for ACRONAL A846 as a function of coalescentaids; and

FIG. 9 is the MFFT plot for ACRONAL A846 as a function of coalescentaids.

In FIGS. 1-4 and 6-9, X1, X2, X3, X4, EB, EB_X and EB+X have thefollowing meanings:

X1=Ethylene glycol soy oil ester,

X2=Propylene glycol soy oil ester,

X3=Diethylene glycol soy oil ester,

X4=Dipropylene glycol soy oil ester,

EB=Ethylene glycol monobutyl ether,

EB_X=derivatives and EB mixture 50:50, and

EB+X=derivatives and EB mixture 50:50.

FIGS. 1-4 and 6-9 are plots of minimum film formation temperature as afunction of % coalescent aid;

FIG. 5 is a plot of the evaporation rate of coalescent aid as a functionof time;

FIG. 10 is a plot of coating resistance and charge transfer resistanceas a function of dry time;

FIG. 11 is a plot of coating capacitance and associated double layercapacitance as a function of dry time;

FIGS. 12-19 are infrared spectra of soybean oil and various coalescentaids;

FIGS. 20-27 are ¹H-NMR spectra of soybean oil and various coalescentaids; and

FIGS. 28-32 are ¹³C-NMR spectra of soybean oil and various coalescentaids.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The water-borne film-forming compositions of the present inventiongenerally contain a continuous aqueous phase and a dispersedfilm-forming phase. In general, they may be formulated to function as apaint, sealant, caulk, adhesive or other coating. Thus, thesefilm-forming compositions may have a wide range of viscosities, e.g.,from about 50 to about 10,000 centipoise; paints, sealants and similarcoatings typically have a viscosity from about 50 to about 10,000centipoise, caulks typically have a viscosity from about 5,000 to about50,000 centipoise, and adhesives typically have a viscosity from about50 to about 50,000 centipoise. In addition, adhesives are formulated forcohesive strength as well as good contact with the substrate upon whichthe film-forming composition is deposited.

The continuous aqueous phase generally comprises at least about 10 wt %water with the amount of water depending upon the application. Forexample, paints, sealants and similar coating compositions willgenerally have at least about 10 wt % water and typically will containabout 20 wt % to about 80 wt % water with differing amounts being usedfor textured, high gloss, semi-gloss, flat, etc. coatings. Caulks willgenerally have at least about 10 wt % water and typically will containabout 10 wt % to about 25 wt % water with differing amounts being usedfor different caulk applications. Adhesives will generally range fromabout 10 wt % to about 80 wt % water and typically will contain about 40wt % to about 60 wt % water with differing amounts being used fordifferent adhesive applications.

The continuous aqueous phase may optionally include one or morewater-soluble organic solvents, i.e., substituted hydrocarbon solvents.For example, modest amounts of ethylene glycol (e.g., 3-5 wt. %) oranother glycol may be included for freeze-thaw protection. In general,however, the proportion of water-soluble organic solvents is preferablyminimized; that is, the continuous aqueous phase preferably containsless than about 20 wt. % organic solvent, more preferably less thanabout 10 wt. % organic solvent, and still more preferably less thanabout 5 wt. % organic solvent, based upon the weight of the continuousaqueous phase and exclusive of any amount which may be present in amicelle or other dispersed phase or material.

The dispersed phase comprises a (i) particulate polymer or an emulsifiedliquid pre-polymer, (ii) a coalescent aid and, optionally, (iii) one ormore additives. In general, the dispersed phase constitutes no more thanabout 90 wt % with the amount of dispersed phase depending upon theapplication. For example, paints, sealants and similar coatingcompositions will generally have no more than about 90 wt % dispersedphase and typically will contain about 20 wt % to about 80 wt %dispersed phase with differing amounts being used for textured, highgloss, semi-gloss, flat, etc. coatings. Caulks will generally have nomore than about 90 wt % dispersed phase and typically will contain about75 wt % to about 90 wt % dispersed phase with differing amounts beingused for different caulk applications. Adhesives will generally rangefrom about 20 wt % to about 90 wt % dispersed phase and typically willcontain about 40 wt % to about 60 wt % dispersed phase with differingamounts being used for different adhesive applications.

In general, the particulate polymer or emulsified liquid pre-polymer isinsoluble in the aqueous phase and is otherwise suitable for use inwater borne film-forming compositions. Because the particulate polymeror emulsified liquid pre-polymer is the component which coalesces toform the desired film, the film-forming composition preferably comprisesat least about 10 wt. %, more preferably at least about 15 wt. %, anddepending for some applications at least about 20 wt. % of a coalescibleparticulate polymer or emulsified liquid pre-polymer.

Preferred particulate polymers are generally high molecular weight (e.g,greater than about 60,000 for latex), crosslinkable, polymer particles.For example, they may be either of the addition type, in particular apolymer or copolymer of one or more α,β-ethylenically unsaturatedmonomers, or of the condensation type, for example, a polyester or apolyamide. Suitable particulate polymers of the addition type includethe polymerization and copolymerization products of styrene, vinylacetate, vinyl toluene, vinyl chloride, vinylidene chloride, butadiene,vinyl hydrocarbons, acrylonitrile, acrylates, and methacrylatecontaining monomers. Suitable condensation type particulate polymersinclude epoxy, urethane, hydrocarbon, silicone, nitrocellulose,polyester, and alkyd polymers. Preferred particulate polymers includeacrylate, methacrylate, styrene and vinyl acetate. Examples of preferredparticulate polymers include the polymerizates or copolymerizates of oneor more of the following: alkyl acrylates such as ethyl acrylate, butylacrylate, 2-ethylhexyl acrylate, as well as other alkyl acrylates, alkylmethacrylates, styrene and vinyl acetate.

In general, smaller particulate polymers are more readily coalesced thanlarger particulate polymers. Accordingly, preferred particulate polymersgenerally have a size of about 3 micrometers or less. For example, forlatex resins, approximately 90 wt. % of the latex particles will have asize less than about 0.2 micrometers.

Preferred emulsified liquid pre-polymers include alkyds, epoxies,nitrocellulose, and urethanes.

The coalescent aid of the present invention preferably comprises anester having the formulaRCOOXwherein

R is hydrocarbyl or substituted hydrocarbyl,

X is hydrocarbyl or substituted hydrocarbyl, and

at least one of R and X contains two or more aliphatic unsaturatedcarbon-carbon bonds (hereinafter “polyunsaturated”).

Preferably, R contains about 1 to about 30 carbon atoms, more preferablyabout 9 to about 25 carbon atoms, and still more preferably about 15 toabout 23 carbon atoms, X contains about 1 to about 30 carbon atoms, morepreferably about 1 to about 18 carbon atoms, and still more preferablyabout 1 to about 6 atoms, and R and X in combination contain no morethan about 35 carbon atoms, and more preferably, R and X, incombination, contain no more than about 30 carbon atoms. In addition, atleast one of R and X preferably contains a conjugated double or triplecarbon-carbon bond (i.e., two or more carbon-carbon double or triplebonds which alternate with carbon-carbon single bonds). For example, theunsaturation may take the form of two conjugated double bonds, aconjugated double bond and triple bond or two conjugated triple bonds.

While the carbon-carbon polyunsaturation may be provided in R or X, itis generally preferred that it be provided at the tail of the ester,i.e., in R. Thus, R is preferably hydrocarbyl or substituted hydrocarbylpossessing at least two aliphatic unsaturated carbon-carbon bonds, morepreferably in conjugation, with R preferably comprising about 5 to about25 carbon, more preferably about 9 to about 25 carbon atoms, and stillmore preferably about 11 to about 23 carbon atoms. If R is substitutedhydrocarbyl, it is preferably substituted with ketone, amide, ester,alcohol, urea, urethane, nitrile functionalities; silyl and aminefunctionalities are preferably avoided and alcohols are preferablyavoided if the number of carbon atoms is less than about 10.

Optionally, the head of the ester, i.e., X, may be polyunsaturatedinstead of the tail of the ester. In this instance, X is preferablyhydrocarbyl or substituted hydrocarbyl possessing at least two aliphaticunsaturated carbon-carbon bonds, more preferably in conjugation with Xpreferably comprising about 5 to about 30 carbon, more preferably about5 to about 25 carbon atoms, and still more preferably about 5 to about24 carbon atoms.

If R is polyunsaturated, X may optionally contain one or more degrees ofcarbon-carbon unsaturation. Stated another way, X may be hydrocarbyl orsubstituted hydrocarbyl optionally possessing one or more degrees ofcarbon-carbon unsaturation. As with R, X may optionally contain at least2 degrees of carbon-carbon unsaturation with the 2 degrees ofcarbon-carbon unsaturation optionally being in conjugation. In oneembodiment of the present invention, for example, X is X′—OH wherein X′is a hydrocarbyl or substituted hydrocarbyl radical comprising about 1to about 8 carbon atoms. Preferably, X′ comprises about 2 to about 6carbon atoms and, in one embodiment X′ possesses at least one degree ofunsaturation. If X or X′ is substituted hydrocarbyl, it is preferablysubstituted with ketone, amide, ester, alcohol, urea, urethane, nitrilefunctionalities; silyl and amine functionalities are preferably avoided.

The polyunsaturated ester of the present invention is preferablysufficiently involatile to avoid categorization as a Volatile OrganicCompound by the United States Environmental Protection Agency. In oneembodiment of the present invention, the coalescent aid is a singleester. In another embodiment of the present invention, the coalescentaid comprises a mixture of esters with at least one of the esters beinga polyunsaturate. In a third embodiment, the coalescent aid comprises apolyunsaturated ester with a conventional coalescent aid such asethylene glycol monobutyl ether (EB, Union Carbide) or2,2,4-trimethyl-1,3 pentanediol monobutyrate (TEXANOL®, Eastman Kodak).Where composition(s) other than polyunsaturated esters are also used asa coalescent aid, it is generally preferred that the polyunsaturatedester comprise at least about 5 wt. %, more preferably at least about 10wt. %, still more preferably at least about 25 wt. %, still morepreferably at least about 50 wt. %, and still more preferably at leastabout 75 wt. %, based upon the total combined weights of thecompositions used as coalescent aids.

The polyunsaturated ester of the present invention may be derived from anatural, genetically engineered or synthetic material such as an oil,fat, lecithin or petroleum product. In a preferred embodiment, thecoalescent aid comprises a polyunsaturated ester derived from an oil ofplant or animal origin (including oils obtained from geneticallyengineered species), such as canola, linseed, soybean, or anothernaturally occurring oil such as one identified in Table I. Examples ofpreferred polyunsaturated esters include methyl ester, ethylene glycolmonoester, diethylene glycol monoester, propylene glycol monoester, anddipropylene glycol monoester derived from the fatty acids of these oils.

TABLE I AVERAGE FATTY ACID AS PERCENT OF TOTAL FATTY ACID Number ofCarbon Atoms * 6 10 12 14 16 18 18 18 18 16 18 22 20-22 20-24 Number ofDouble Bonds VEGETABLE OIL 0 0 0 0 0 0 1 2 3 1 1 1 ** 3 Castor 85 1.02.0 2.0 5.0 90.0 Corn 124 13.0 4.0 29.0 54.0 Cottonseed 107 22.0 2.021.0 54.0 Crambe 94 3.0 2.0 18.0 10.0 5.0 56.0 3.0 2.0 Linseed 185 6.04.0 20.0 17.0 53.0 Mustard 120 2.0 24.0 20.0 6.0 43.0 5.0 Olive 80 8.02.0 82.0 8.0 Oiticica¹ 150 7.0 6.0 5.0 Peanut 90 7.0 6.0 60.0 22.0 5.0Rapeseed 101 2.0 2.0 16.0 16.0 8.0 45.0 6.0 4.0 Rice Bran 102 17.0 1.047.0 35.0 Safflower 141 6.0 2.0 13.0 79.0 Sardine, Pilchard 190 14.0 3.010.0 15.0 12.0 41.0 Sesame 110 9.0 4.0 46.0 41.0 Soybean 130 8.0 6.028.0 50.0 8.0 Sunflower 139 6.0 2.0 26.0 66.0 Tung (Regular)² 165 4.01.0 5.0 8.0 Tung (African)³ 160 4.0 1.0 9.0 15.0 Walnut (English) 1509.0 1.0 16.0 60.0 13.0 * Iodine Number; ** polyethenoic acids; ¹contains82% licanic acid; ²contains 82% eleostearic acid; ³contains 71%elestearic acid

The fatty acid ester glycols may be prepared by transesterificationreactions between various glycols and fatty acids from soybean and otheroils of plant or animal origin in the presence of a catalyst. Suitablecatalysts include bases such as lithium hydroxide, tin oxides, tincatalysts, and calcium oxide with the reaction temperature generallybeing about 100 to about 200 EC. In a preferred embodiment, the glycolused in the reaction is ethylene glycol, propylene glycol, diethyleneglycol or dipropylene glycol with the reaction being carried out withabout 6 moles of glycol per mole of soybean oil in the presence of abasic catalyst at a temperature of about 190° C. under nitrogenatmosphere. After reaction, the excess glycol is extracted with waterseveral times. The soy oil ester is extracted with ethyl ether anddried, for example, with magnesium sulfate. Then the ethyl ether isdistilled off. The reaction equation is given below.

where R is unsaturated hydrocarbon chain having 17 carbons

-   -   R′ is a group of the formula —C₂H₄— for ethylene glycol        -   —C₃H₆— for propylene glycol        -   —C₂H₄O—C₂H₄— for diethylene glycol        -   —C₃H₆O—C₃H₆— for dipropylene glycol

The amount of coalescent aid needed to assist in film formation dependson the viscosity of the film-forming composition, the temperature atwhich the composition is being applied, the glass transition temperatureof the film-former, and the minimum film formation temperature of thefilm-former. In general, the amount of coalescent will be proportionalto the amount and type of resin used with ratios in the range of about0.1 wt % to about 50 wt. % (based upon the weight of the dry resin),typically in the 1 wt. % to about 4 wt. % range (based upon the weightof the dry resin).

Any coalescent aid which remains in the film will act as a plasticizer,keeping the glass transition temperature low unless it haspolyunsaturation which will allow it to be air oxidized and oligomerizedwhich results in the coalescent aid becoming more of a resin and less ofa plasticizer. Thus, the glass transition temperature is in partrecovered. In general, the greater degree of unsaturation of thecoalescent aid the more glass transition temperature recovery can beexpected. Where a mixture of materials are used as the coalescent aid,therefore, it is generally preferred that the polyunsaturated acid(s)comprise at least about 5 wt. %, more preferably at least about 25 wt.%, still more preferably at least about 40 wt. % and still morepreferably at least about 50 wt. % of the coalescent aid.

Trace amounts of the polyunsaturated ester coalescent aid of the presentinvention may be dissolved in the continuous aqueous phase; that is,preferably less than about 10 wt. %, more preferably less than 5 wt. %,still more preferably less than 1 wt. %, and for some embodiments stillmore preferably less than about 0.5 wt. % of the polyunsaturated esteris dissolved in the continuous aqueous phase, based upon the weight ofthe continuous aqueous phase. The predominant proportion of thepolyunsaturated ester coalescent aid is thus preferably dissolved in thedispersed particulate polymer or liquid pre-polymer. Preferably at least80 wt. %, more preferably at least 90 wt. %, more preferably at least 95wt. %, and still more preferably at least 99 wt. % of thepolyunsaturated ester coalescent aid is dissolved in the dispersedparticulate polymer or liquid pre-polymer. Depending upon the type andamount of surfactants included in the film-forming composition, arelatively small fraction of the polyunsaturated ester coalescent aidmay additionally be emulsified in the continuous aqueous phase and foundin micelles along with surfactant.

The film-forming composition of the present invention may also containvarious conventional additives which may be in the dispersed and/orcontinuous phases. Such additives include thickening agents such ascarboxymethylcellulose sold by Aquilon under the trade designationNATRASOL 250 and thickeners sold under the trade designation M-P-A 1075by Rheox, pH modifiers such as ammonium hydroxide and N,N-dimethylethanolamine, defoaming agents such as mineral oil or silicone oils,wetting agents such as a nonionic surfactant sold by AKZO under thetrade designation INTERWET 43 and a nonionic surfactant sold by Rohm &Haas under the trade designation Triton X100, algicides such asorganotin compounds and tetrachloroisophthalonitrile, fungicides such astributyl tin oxide, and 3-iodo-2-propynyl butyl carbamate, dispersantssuch as lecithin and an anionic dispersant sold under the tradedesignation BUSPERSE 39 by Buckman, ultraviolet inhibitors such as abenztriazol UV inhibitor sold under the trade designation TINUVIN 328 byCiba-Geigy and a hindered amine UV inhibitor sold under the tradedesignation by TINUVIN 123 by Ciba-Geigy, flow and leveling agents suchas a polyacrylate sold under the trade designation BYK 354 by BYK-Chemieand a polysiloxane copolymer sold under the trade designation BYK 310 byBYK-Chemie, flash rust inhibitors such as an inhibitor sold under thetrade designation RAYBO 63 by Raybo or a barium metaborate rustinhibitor sold under the trade designation BUSAN 11M1 by Buckman, andfreeze/thaw inhibitors such as ethylene glycol. Additional additivesinclude driers such as cobalt driers carboxylate salts (0.0 to 0.15 wt.% Co based on the coalescent aid) and manganese driers carboxylate salts(0.0 to 0.15 wt. % based on the coalescent aid), accelerators such as1,10-phenanthroline (0 to 0.2% based on the coalescent aid) and2,2-bipyridine (0 to 0.2% based on the coalescent aid), andanti-skinning agents such as butanone oxime (0-11 lb/100 galformulation). When present and depending upon the application for thefilm-forming composition, these additives will generally not constitutemore than about 10 wt. % of the film-forming composition and willtypically constitute about 3 wt. % to about 10 wt. % of the film-formingcomposition.

The film-forming composition is formed by conventional methods used toprepare paints, adhesives, except that the polyunsaturated ester of thepresent invention is substituted, at least in part, for a conventionalcoalescent aid. The resulting film-forming composition can easily beapplied conventionally using a brush, roller, or like means and requiresno unusual methods of drying to form the desired film. Thus, filmsformed from the composition of the present invention may be dried underambient conditions. Furthermore, the film-forming composition may beapplied to a variety of materials.

Definitions

As used herein, the term “hydrocarbyl” shall mean a radical consistingexclusively of carbon and hydrogen. The hydrocarbyl may be branched orunbranched, saturated or unsaturated. Suitable hydrocarbyl moietiesinclude alkyl, alkenyl, alkynyl, and aryl moieties. They also includealkyl, alkenyl, alkynyl, and aryl moieties substituted with othersaturated or unsaturated hydrocarbyl moieties such as alkaryl, alkenaryland alkynaryl. Preferably, the hydrocarbyl does not include an arylmoiety and except as otherwise indicated herein, the hydrocarbylmoieties preferably comprises up to about 25 carbon atoms.

The aryl moieties described herein contain from 6 to 20 carbon atoms andinclude phenyl. They may be hydrocarbyl substituted with the varioussubstituents defined herein. Phenyl is the more preferred aryl.

The term “substituted hydrocarbyl” shall mean a hydrocarbyl radicalwherein at least one hydrogen atom has been substituted with an atomother than hydrogen or carbon, including moieties in which a carbonchain atom is substituted with a hetero atom such as nitrogen, oxygen,silicon, phosphorous, boron, sulfur, or a halogen atom. Thesesubstituents include hydroxy; lower alkoxy such as methoxy, ethoxy,butoxy; halogen such as chloro or fluoro; ethers; esters; heteroarylsuch as furyl or thienyl; alkanoxy; acyl; acyloxy; nitro; amino; andamido. In general, however, amines and silyl radicals are preferablyexcluded.

The acyl moieties and the acyloxy moieties described herein containhydrocarbyl, substituted hydrocarbyl or heteroaryl moieties. In general,they have the formulas —C(O)G and —OC(O)G, respectively, wherein G issubstituted or unsubstituted hydrocarbyl, hydrocarbyloxy,hydrocarbylamino, hydrocarbylthio or heteroaryl.

This invention will be further illustrated by the following Examplesalthough it will be understood that these Examples are included merelyfor purposes of illustration and are not intended to limit the scope ofthe invention.

EXAMPLES

Test Procedures

The following test procedures were used to generate the data reported inthe examples below:

Minimum Film Formation Temperature Measurement

The method used for measuring MFFT followed ASTM Method D2354-68.Minimum film formation temperatures for ten different coalescent aidformulated latexes were measured. Four replicate measurements wereperformed for the same latex and were then averaged.

Blocking Resistance Testing

The procedure employed to evaluate block resistance followed ASTM MethodD4946-89. A 6 mil thick film of latex was drawn down on a Leneta chartand dried for 7 days room temperature. The dried films were cut intosquares ˜1.5×1.5 inch² and the squares were placed together with face toface contacted each other. The face-to-face specimens were placed in a35° C. oven on the flat aluminum tray. A 1000 kg weight on a No. 8stopper were placed on the specimens to yield a pressure of about 1.8psi (127 g/cm²). After exactly 30 min, the stopper and weight wereremoved. The sample was allowed to cool for 30 min at room temperaturebefore determining the block resistance according to the followingscale:

10 . . . no tack

9 trace tack

8 very slight tack

7 very slight to slight tack

6 slight tack

5 moderate tack

4 very tacky, no seal

3 5-25% seal

2 25-50% seal

1 50-75% seal

0 75-100% seal

Adhesion Testing

The method used to for determining adhesion followed ASTM MethodD3359-92a. A 6 mil wet film thickness of latex was drawn down on analuminum panel and dried for 7 days at room temperature. After drying,an area was selected that was free of blemishes and minor surfaceimperfections. Eleven cuts in each direction, orthogonal, were madethrough the film to the substrate in one steady motion using sufficientpressure on the cutting tool to have the cutting edge reach thesubstrate. Make all cuts about ¾ inch (20 mm). Place the center of thetape over the grid and in the area of the grid smooth into place by afinger. To ensure good contact with the film, rub the tape firmly withthe eraser. The opacity change of the tape was a useful indication ofwhen good contact has been made. Within 90 sec of application, removethe tape by seizing the free end and rapidly pull back upon itself at anangle of approximately 180°. Inspect the grid area for removal ofcoating from the substrate. Rate the adhesion in accordance with thefollowing scale:

-   -   5B The edges of the cuts are completely smooth; none of the        squares of the lattice is detached.    -   4B Small flakes of the coating are detached at intersections;        less than 5% of the area is affected.    -   3B Small flakes of the coating are detached along edges and at        intersections of cuts. The area affected is 5-15% of the        lattice.    -   2B The coating has flaked along the edges and on parts of the        squares. The area affected is 15-35% of the lattice.    -   1B The coating has flaked along the edges of cuts in large        ribbon and whole squares have detached. The area affected is        35-65% of the lattice.    -   0B Flaking and detachment worse than grade 1B.        Freeze-Thaw and Thermal Stability

Three, 500 grams cans of paint had been prepared for each system beinginvestigated. One was for freeze-thaw stability test, one for thermalstability test and the other one for control. The control samples werestored at room temperature.

For thermal stability testing, paint cans were put in oven at 50° C. for17 hours, then was taken out to cool at room temperature for 7 hours.This is a cycles of testing. Repeat testing for at least 5 cycles andobserved a physical appearance of paints in cans. Gloss and hiding powerwere measured and compared with those from control.

For freeze-thaw stability testing, one cycle composes of 17 hours offreezing in a refrigerator at −8° C. and 7 hours of thawing at roomtemperature. At least 5 cycles had been taken. The physical appearanceof paints were observed. Gloss and hiding power were measured andcompared with those from control.

Gloss and Hiding Power

Each paint formulation was drawn down onto a Lenetta chart with filmthickness of 3 mils, and let dry at room temperature for two days beforegloss (@60°) and hiding power measurement would be taken by glossmeterand color computer, respectively.

Scrub Resistance Testing

Each paint formulation was drawn down onto a plastic panel with 6 mildraw down bar and let dry at room temperature for 7 days before testing.The testing including scrub media preparation was by the methoddescribed in ASTM D 2486-89.

Pencil Hardness Testing

The method used for determining hardness followed ASTM Method D3363-92a.A 6 mil thickness film of latex was drawn down on an aluminum panel anddried for 7 days at room temperature. After drying, an area was selectedthat was free of blemishes and minor surface imperfections. The pencilswas prepared by polishing the tip of the pencil in circular motion toget a sharp edge. The panel was placed on a firm horizontal surface. Thepencil was held firmly against the film at a 45° angle (point away fromoperator) and pushed away from the operator in a ¼ in stroke. The pencilnumber that does not cut into or gauge the paint film was reported.

Evaporation Rate

Three samples of each coalescent aid was weighed into aluminum pans. Alltest samples were kept at room temperature. The percentage of weightloss of each coalescent aid was measured as a function of time.

Surface Tension

Surface tension was determined by the ring method tensiometer accordingto ASTM D 1331-89.

Hydrophilic Lipophilic Balance

Hydrophilic lipophilic balance (HLB) values were calculated fromEquation 1 based on ethylene oxide moiety in the molecule.

$\begin{matrix}{{HLB} = \frac{\%\mspace{14mu}{{wt}.\mspace{14mu}{of}}\mspace{14mu}{ethylene}\mspace{14mu}{oxide}\mspace{14mu}{in}\mspace{14mu}{the}\mspace{14mu}{molecule}}{5}} & {{Equation}\mspace{14mu} 1}\end{matrix}$Solubility Parameters

Solubility parameter values were calculated according to the HansenMethod from the Handbook of Solubility Parameters.

Density

Density was determined according to ASTM D-1475.

¹³C NMR Spectra

¹³C NMR spectra were determined without solvent added at roomtemperature in 5-mm inner-diameter tubes.

¹H NMR Spectra

¹H NMR spectra were operated with neat liquid reaction products.

Example 1

Coalescent efficiency using a low Tg latex polymer with various soybeanoil esters.

Master batch formulation for MFFT testing of vinyl acetate latex,FLEXBOND 325, and vinyl acrylic latex, UCAR 379G is given in the Tablebelow.

Formulation for studying MFFT for low Tg latex polymers formulationsolid content lb. gal. lb. gal. H2O 286.35 34.38 0.00 0.00 PG 43.20 4.990.00 0.00 X-102 1.98 0.22 1.98 0.22 RM825 1.82 0.21 0.46 0.05 WET2600.87 0.10 0.87 0.10 AMP95 1.98 0.25 0.00 0.00 low Tg resins 430.22 47.54236.62 24.44 DREWPLUS 493 2.38 0.32 0.36 0.13 H2O 99.88 11.99 0.00 0.00Total 868.69 100.00 240.29 24.94 wt/gal 8.69 % sol/wt 27.66 % sol/vol.24.94 Note: In the batch formulations PG = propylene glycol X-102 =Triton X-102: surfactant (Union Carbide) RM = Acrysol RM 825:associative thickener (Rohm & Haas) WET260: wetting agent (TegoChemical) AMP 95: pH modifier (Angus) Drewplus L-493: defoamer (DrewChemical)

To 50 grams portion of master batch was added the coalescent aids at thefollowing levels: 0.25 g (0.5%); 0.375 g (0.75%); 0.5 g (1.0%). Thesamples were equilibrated for 48 hours prior to determination of theminimum film formation temperature using a MFFT BAR-90 (RhopointInstrumentation Ltd, England).

As illustrated by FIG. 1, all new soy oil glycol ester coalescent aidsof this invention show a potential in lowering the minimum filmformation temperature of latex polymer, FLEXBOND 325 similar tocommercial coalescent aids TEXANOL® and EB.

As shown in FIG. 2, all new soy oil glycol ester coalescent aids of thisinvention show a capability in lowering the minimum film formationtemperature of latex polymer, UCAR 379G, better than the commercialcoalescent aid TEXANOL®, and also give a similar trend to the commercialcoalescent aid EB.

Example 2

Coalescent efficiency using a high Tg latex polymer with various soybeanoil glycol esters.

Master batch formulation for MFFT testing of high Tg acrylic latex,ACRONAL A846, is given in the Table below.

Formulation for studying MFFT for ACRONAL A846 formulation solid contentlb. gal. lb. gal. H2O 278.29 33.41 0.00 0.00 PG 42.40 4.90 0.00 0.00X-102 5.09 0.57 5.09 0.57 RM825 3.85 0.44 0.96 0.10 WET kl245 7.71 0.897.71 0.89 AMP95 0.00 0.00 0.00 0.00 Acronal486 418.60 47.84 209.30 22.82DREWPLUS 2.16 0.29 0.32 0.12 H2O 97.13 11.66 0.00 0.00 Total 855.23100.00 223.38 24.50 wt/gal 8.55 % sol/wt 26.12 % sol/vol. 24.50 WETkl245: wetting agent

To 50 grams portion of master batch was added the coalescent aids at thefollowing levels: 0.25 g (0.5%); 0.375 g (0.75%); 0.5 g (1.0%). Thesamples were equilibrated for 48 hours prior to determination of theminimum film formation temperature using a MFFT BAR-90 (RhopointInstrumentation Ltd, England).

As illustrated by FIG. 3, all new soy oil glycol ester coalescent aidsof this invention show a capability in lowering the minimum filmformation temperature of high Tg acrylic latex polymer, ACRONAL A846,better than the commercial coalescent aid EB, and also give a similartrend to the commercial coalescent aid TEXANOL® at every level ofcoalescent aids added.

Master batch formulation for MFFT testing of high Tgpolystyrene/polymethyl methacrylate latex, UCAR 430, is given in theTable below.

Formulation for studying MFFT for UCAR 430 formulation solid content lb.gal. lb. gal. H2O 288.56 34.64 0.00 0.00 PG 43.96 5.08 0.00 0.00 X-1025.28 0.59 5.28 0.59 RM825 4.00 0.46 1.00 0.10 WET kl245 7.99 0.92 7.990.92 AMP95 0.00 0.00 0.00 0.00 UCAR430 434.03 49.89 195.31 21.23DREWPLUS 2.24 0.30 0.34 0.12 H2O 67.62 8.12 0.00 0.00 Total 853.68100.00 209.92 22.97 wt/gal 8.54 % sol/wt 24.59 % sol/vol. 22.97

To 50 gram portion of master batch was added the coalescent aids at thefollowing levels: 0.25 g (0.5%); 0.375 g (0.75%); 0.5 g (1.0%). Thesamples were equilibrated for 48 hours prior to determination of theminimum film formation temperature using a MFFT BAR-90 (RhopointInstrumentation Ltd, England).

As shown in FIG. 4, all new soy oil glycol ester coalescent aids of thisinvention show a capability in lowering the minimum film formationtemperature of high Tg PS/PMMA latex polymer, UCAR 430, better than thecommercial coalescent aid EB, and also give a similar trend to thecommercial coalescent aid TEXANOL® at every level of coalescent aidsadded.

Example 3

Physical properties of paint formulations with a low Tg latex polymerwith ethylene glycol soybean oil esters and TEXANOL®.

Semigloss and flat paint formulations of low Tg, vinyl acetate latex,FLEXBOND 325, have been prepared for physical testing. The formulationswith TEXANOL® are given in the Tables below.

GLOSS PAINT/FLEXBOND325/TEXANOL ® formulation lb. gal H2O 50.58 52.58 PG58.28 6.74 X-102 2.01 0.22 RM825 15.70 1.80 TAMOL850 8.29 0.84 WET2604.51 0.52 AMP95 3.62 0.46 TP-900 224.91 6.75 ATOMITE 73.46 3.25 FXBD325582.93 64.06 TEXANOL ® 18.92 2.39 DREWPLUS 1.91 0.26 H2O 55.19 6.62Total 1100.30 100.00 wt/gal 11.00 % sol/wt 57.46 % sol/vol. 44.39 % PVC22.55 TP-900: Titanium ATOMITE: Calcium Carbonate

FLAT PAINT/FLEXBOND325/TEXANOL ® formulation lb. gal H2O 141.83 17.03 PG43.31 5.01 X-102 2.17 0.24 RM825 20.77 2.39 TAMOL850 18.08 1.83 WET2604.85 0.56 AMP95 2.17 0.28 TP-900 241.98 7.27 ATOMITE 194.88 8.63 FXBD325433.07 47.59 TEXANOL ® 14.07 1.78 DREWPLUS 2.06 0.27 H2O 59.37 7.13Total 1178.61 100.00 wt/gal 11.79 % sol/wt 58.80 % sol/vol. 42.22 % PVC37.66 FXBD 325 = Flexbond 325

The formulations with ethylene glycol derivative soybean oil glycolesters are given in the Tables below.

GLOSS PAINT/FLEXBOND325/SYNTHETIC COALESCENT AID formulation (by weight)formulation (by volume) lb. gal. H2O 77.67 9.32 PG 56.05 6.48 X-102 1.840.20 RM825 17.42 2.00 TAMOL850 7.97 0.81 WET260 4.34 0.50 AMP95 4.240.54 TP-900 216.28 6.49 ATOMITE 70.64 3.13 FXBD325 560.56 61.60EG-DERIV(X1) 18.19 2.30 DREWPLUS 1.84 0.25 H2O 53.07 6.37 Total 1090.09100.00 wt/gal 10.90 % sol/wt 55.81 % sol/vol. 42.73 % PVC 22.52EG-DERIV(X1) = Ethylene glycol soy oil ester

FLAT PAINT/FLEXBOND325/SYNTHETIC COALESCENT AID formulation (by weight)formulation (by volume) lb. gal. H2O 142.58 17.12 PG 43.53 5.03 X-1022.18 0.24 RM825 15.96 1.83 TAMOL850 18.18 1.84 WET260 4.88 0.56 AMP952.18 0.28 TP-900 243.25 7.30 ATOMITE 195.91 8.68 FXBD325 435.34 47.84EG-DERIV (X1) 14.15 1.79 DREWPLUS 2.37 0.32 H2O 59.69 7.17 Total 1180.18100.00 wt/gal 11.80 % sol/wt 58.93 % sol/vol. 42.33 % PVC 37.76

Semigloss and flat paint formulations of low Tg vinyl acrylic latex,UCAR 379G, have been prepared for physical testing. The formulationswith TEXANOL® are given in the Tables below.

GLOSS PAINT/UCAR379G/TEXANOL ® formulation (by weight) formulation (byvolume) lb. gal. H2O 37.19 4.47 PG 72.80 8.42 X-102 2.01 0.22 RM82517.08 1.96 TAMOL850 7.89 0.80 WET260 4.53 0.52 AMP95 1.41 0.18 0.00TP-900 226.02 6.79 ATOMITE 74.15 3.29 0.00 UCAR379 587.51 64.92TEXANOL ® 33.45 4.23 DREWPLUS 1.93 0.26 H2O 32.88 3.95 Total 1098.86100.00 wt/gal 10.99 % sol/wt 57.95 % sol/vol. 44.91 % PVC 22.43

FLAT PAINT/UCAR379G/TEXANOL ® formulation (by weight) formulation (byvolume) lb. gal. H2O 132.28 15.88 PG 54.86 6.34 X-102 2.21 0.25 RM82517.19 1.98 TAMOL850 18.47 1.87 WET260 4.98 0.58 AMP95 1.11 0.14 0.00TP-900 248.28 7.46 ATOMITE 199.08 8.82 0.00 UCAR379 442.41 48.89TEXANOL ® 25.22 3.19 DREWPLUS 2.12 0.28 H2O 36.12 4.34 Total 1184.33100.00 wt/gal 11.84 % sol/wt 59.78 % sol/vol. 43.19 % PVC 37.68

The formulations with ethylene glycol soybean oil esters are given inthe Tables below

GLOSS PAINT/UCAR379G/SYNTHETIC COALESCENT AID formulation (by weight)formulation (by volume) lb. gal. H2O 82.21 9.87 PG 68.37 7.90 X-102 1.890.21 RM825 18.91 2.17 TAMOL850 7.94 0.80 WET260 4.48 0.52 AMP95 1.320.17 0.00 TP-900 212.27 6.37 ATOMITE 69.63 3.09 0.00 UCAR379 551.7660.97 EG DERIV (X1) 31.41 3.98 DREWPLUS 1.82 0.24 H2O 30.88 3.71 Total1082.90 100.00 wt/gal 10.83 % sol/wt 55.33 % sol/vol. 42.29 % PVC 22.37

FLAT PAINT/UCAR379G/SYNTHETIC COALESCENT AID formulation (by weight)formulation (by volume) lb. gal. H2O 133.08 15.98 PG 55.19 6.38 X-1022.23 0.25 RM825 11.57 1.33 TAMOL850 19.14 1.93 WET260 5.01 0.58 AMP951.11 0.14 0.00 TP-900 249.77 7.50 ATOMITE 200.28 8.87 0.00 UCAR379445.07 49.18 EG DERIV (X1) 25.37 3.21 DREWPLUS 2.14 0.29 H2O 36.34 4.36Total 1186.29 100.00 Wt/gal 11.86 % sol/wt 59.94 % sol/vol. 43.32 % PVC37.80Results

The physical property testing results are shown in the Table below.

FREEZE-THAW STABILITY AND THERMAL STABILITY TESTING Viscosity physical(cps) Hiding power gloss @ 60° appearance gloss/ucar/TEXANOL ® Control1785 94.4 20.7/17   no settling Oven 1985 94.0 17.7/14.3 no settlingFreezer 1775 94.8 20.5/17.4 no settling gloss/flexbond/TEXANOL ® Control1735 95.2 26.7/24.2 no settling Oven 1715 94.4 25.3/21.4 no settlingFreezer 1570 95.4 27.8/24.2 no settling flat/ucar/TEXANOL ® Control 134595.8 3.6/3.4 no settling oven 1375 94.9 3.4/3.3 no settling freezer 126095.0 3.5/3.3 no settling flat/flexbond/TEXANOL ® control 1965 94.24.5/4.9 no settling oven 1885 93.8 4.2/4.6 no settling freezer 1505 94.34.6/4.8 no settling gloss/ucar/synthetic coalescent aid Control 200593.9 21.0/17.7 no settling oven 1610 92.7 18.8/16.4 no settling freezer2235 93.7 21.1/18.4 no settling

FREEZE-THAW STABILITY AND THERMAL STABILITY TESTING cont. Viscosityphysical (cps) Hiding power gloss @ 60° appearancegloss/flexbond/synthetic coalescent aid control 1170 95.3 26.8/23.6 nosettling oven 1170 94.4 25.3/20.7 no settling freezer 1120 95.126.8/22.6 no settling flat/ucar/synthetic coalescent aid control 198594.9 5.1/4.3 no settling oven 2135 94.1 4.7/4.0 no settling freezer 187093.9 4.8/4.2 no settling flat/flexbond/synthetic coalescent aid control1580 94.2 5.4/5.2 no settling oven 1540 93.8 4.7/4.8 no settling freezer1390 94.7 5.4/5.3 no settling

The incorporation of ethylene glycol soy oil ester as a coalescent aidin paint formulations with low Tg latex polymers exhibited thermalstability and freeze-thaw stability similar to commercial coalescentaid, TEXANOL® (Eastman Kodak). There was no settling in all paintformulations. The gloss and hiding power were stable in all paintformulation after freeze-thaw and heat-cool for at least 5 cycles.

SCRUB RESISTANCE TESTING RESULTS Scrub resistant (cycles)gloss/ucar/TEXANOL ® >3000 gloss/flexbond/TEXANOL ® >3000flat/ucar/TEXANOL ® >3000 flat/flexbond/TEXANOL ® >3000gloss/ucar/synthetic coalescent aid >3000 gloss/flexbond/syntheticcoalescent aid >3000 flat/ucar/synthetic coalescent aid >3000flat/flexbond/synthetic coalescent aid >3000

The scrub resistance of paint formulations formulated with ethyleneglycol soy oil ester as a coalescent aid showed an excellent scrubresistance similar to paint formulations with commercial coalescent aid,TEXANOL® (Eastman Kodak). Both of low Tg latex polymers used in thisinvention gave the same result in scrub resistance.

BLOCKING RESISTANCE TESTING RESULTS Blocking resistant ratingPerformance SEMIGLOSS Flexbond325 + TEXANOL ® 2.0 25-50% sealFlexbond325 + Methyl Ester 3.0-4.0 Poor-fair Flexbond325 + EG-derivative6.0-7.0 Good-very good Ucar379g + TEXANOL ® 3.0-4.0 Poor-fair Ucar379g +Methyl Ester 3.0 Poor Ucar379g + EG-derivative 5.0 Fair FLATFlexbond325 + TEXANOL ® 7.0 Good-very good Flexbond325 + Methyl Ester5.0-6.0 Fair-good Flexbond325 + EG-derivative 6.0 Good Ucar379g +TEXANOL ® 7.0-8.0 Good-very good Ucar379g + Methyl Ester 6.0-7.0 GoodUcar379g + EG-derivative 4.0-5.0 Fair

Semigloss paint formulation with ethylene glycol soy oil ester as acoalescent aid showed better blocking resistance than paint formulationwith comparative coalescent aid, TEXANOL® (Eastman Kodak). Flat paintformulation with ethylene glycol soy oil ester as a coalescent aidshowed poorer blocking resistance than paint formulation withcomparative coalescent aid, TEXANOL® (Eastman Kodak). Both low Tg latexpolymers used in this invention provided the same trend of blockingresistance performance.

PENCIL HARDNESS TEST RESULTS Hardness rating GLOSS Flexbond325 +TEXANOL ® 5B Flexbond325 + X1 5B-6B ucar379g + TEXANOL ® 6B ucar379g +X1 OVER 6B FLAT Flexbond325 + TEXANOL ® 4B Flexbond325 + X1 4B-5Bucar379g + TEXANOL ® 5B-6B ucar379g + X1 6B

Hardness of film from paint formulation with ethylene glycol soy oilester as a coalescent aid was lower in hardness than the film from paintformulated with the commercial coalescent aid, TEXANOL® (Eastman Kodak).Both of low Tg latex polymers used in this invention provided lesshardness with the new coalescent aid.

ADHESION TEST RESULTS Surface of cross-cut area from which flaking hasoccurred on scratched panel with epoxy primer GLOSS Flexbond325 +TEXANOL ® >65% >65% Flexbond325 + me-ester >65% >65% Flexbond325 +X1 >65% >65% Ucar379g + TEXANOL ® >65% >65% Ucar379g +Me-ester >65% >65% ucar379g + X1 >65% >65% FLAT Flexbond325 +TEXANOL ® >65% >65% Flexbond325 + me-ester >65% >65% Flexbond325 +X1 >65% >65% Ucar379g + TEXANOL ® >65% >65% Ucar379g +Me-ester >65% >65% Ucar379g + X1 >65% >65%

The semigloss and flat paint formulation, with both low Tg latexpolymers and ethylene glycol soy oil ester as a coalescent aid,exhibited poor performance in adhesion of paint film both on scratchedaluminum panel and on epoxy-primed aluminum panel. The same poorperformance occurred with commercial coalescent aid, TEXANOL® (EastmanKodak).

Example 4

Physical properties of paint formulations with a high Tg latex polymerwith ethylene glycol soybean oil esters and TEXANOL®. Only the ethyleneglycol soy oil ester derivative has been incorporated into a paintformulation for physical testing relative to the commercial coalescentaids, TEXANOL® (a commercial coalescent aid), and EB.

Semigloss paint formulation of high Tg acrylic latex, ACRONAL A846, hasbeen prepared for physical testing. The formulations with TEXANOL® aregiven in the Table below.

ACRONAL846/TEXANOL ® Formulation (by weight) formulation (by volume) lb.gal. H2O 75.18 9.03 PG 63.05 7.29 X-102 6.57 0.73 RM825 16.05 1.84TAMOL850 2.41 0.24 WET KL245 12.81 1.48 AMP95 0.14 0.02 TP-900 169.755.10 ATOMITE 98.76 4.38 ACRONAL A846 540.11 61.73 TEXANOL ® 27.07 3.43DREWPLUS L493 5.25 0.70 H2O 33.64 4.04 Total 1050.79 100.00 wt/gal 10.51% sol/wt 53.62 % sol/vol. 41.88 % PVC 22.62

The formulations with ethylene glycol soybean oil esters are given inthe Table below.

ACRONAL846/EG Formulation (by weight) formulation (by volume) lb. gal.H2O 75.57 9.07 PG 63.38 7.33 X-102 6.61 0.74 RM825 11.48 1.32 TAMOL8502.42 0.24 WET KL245 12.87 1.49 AMP95 0.14 0.02 TP-900 170.63 5.12ATOMITE 99.27 4.40 ACRONAL A846 542.91 62.05 EG-derivative 27.21 3.46DREWPLUS L493 5.27 0.70 H2O 33.82 4.06 Total 1051.58 100.00 wt/gal 10.52% sol/wt 56.34 % sol/vol. 45.44 % PVC 20.95

Semigloss paint formulation of high Tg PS/PMMA latex, UCAR 430, has beenprepared for physical testing. The formulations with ethylene glycolsoybean oil esters or TEXANOL® are given in the Tables below.

UCAR430/TEXANOL ® Formulation (by weight) formulation (by volume) lb.gal. H2O 79.51 9.55 PG 55.69 6.44 X-102 6.71 0.75 RM825 22.32 2.57TAMOL850 3.05 0.31 WET KL245 9.67 1.12 AMP95 0.28 0.04 TP-900 162.604.88 ATOMITE 89.43 3.96 UCAR430 548.78 63.08 TEXANOL ® 36.99 4.68DREWPLUS L493 2.56 0.34 H2O 19.11 2.29 1036.70 100.00 wt/gal 10.37 %sol/wt 50.38 % sol/vol. 38.62 % PVC 22.90

UCAR430/EG formulation (by weight) formulation (by volume) lb. gal H2O80.01 9.61 PG 56.04 6.48 X-102 6.75 0.75 RM825 17.51 2.01 TAMOL850 3.070.31 WET KL245 9.74 1.13 AMP95 0.29 0.04 TP-900 163.62 4.91 ATOMITE89.99 3.99 UCAR430 552.22 63.47 EG-derivative 37.22 4.74 DREWPLUS L4931.96 0.26 H2O 19.23 2.31 1037.64 100.00 wt/gal 10.38 % sol/wt 54.10 %sol/vol. 43.44 % PVC 20.49Results

The physical property testing results are shown in Table below.

FREEZE-THAW AND THERMAL STABILITIES Semigloss high physical Tg latexhiding power gloss @ 60° appearance Ucar 430 + TEXANOL ® Control 9226.6/21.1 no settling Oven 90 21.0/17.0 no settling Freezer 91.526.6/21.2 no settling Ucar 430 + EG-derivative Control 93 33.9/25.9 nosettling Oven 92 33.1/24.2 no settling Freezer 93 33.0/26.6 no settlingAcronal A846 + TEXANOL ® Control 94 29.5/23.3 no settling Oven 9531.2/24.8 no settling Freezer 94 29.1/28.4 no settling Acronal A846 +EG-derivative Control 94 34.6/26.1 no settling Oven 95 35.3/18.7 nosettling Freezer 95 34.8/24.5 no settling

From the results, the incorporation of ethylene glycol soy oil ester asa coalescent aid in paint formulations with high Tg latex polymersshowed thermal stability and freeze-thaw stability similar to commercialcoalescent aid, TEXANOL® (Eastman Kodak). There was no settling in allpaint formulations. The gloss and hiding power were stable in all paintformulation after freeze-thaw and heat-cool for at least 5 cycles. Paintformulation with the new coalescent aid manifested the improvement ingloss relatively to conventional coalescent aid incorporatedformulation.

SCRUB RESISTANCE TESTING RESULTS Semigloss paint Scrub resistance(cycles) Acronal A846 + TEXANOL ® 748 Acronal A846 + Methyl Ester 782Acronal A846 + EG-derivative 995 Ucar 430 + TEXANOL ® 687 Ucar 430 +Methyl Ester 755 Ucar 430 + EG-derivative 783

The scrub resistance of paint formulation with ethylene glycol soy oilester as a coalescent aid show better scrub resistance than paintformulation with commercial coalescent aid, TEXANOL® (Eastman Kodak).Both of high Tg latex polymers used in this invention gave the sametrend in scrub resistance.

BLOCKING RESISTANCE TESTING RESULTS Blocking resistance ratingPerformance Acronal A846 + TEXANOL ® 5.0-6.0 Fair-good Acronal A846 +Methyl Ester 5.0-6.0 Fair-good AcromalA846 + EG-derivative 6.0-7.0Good-very good Ucar 430 + TEXANOL ® 8.0 Very good Ucar 430 + MethylEster 8.0 Very good Ucar 430 + EG-derivative 9.0 Excellent

Paint formulation with ethylene glycol soy oil ester as a coalescent aidshowed better blocking resistance than paint formulation with thecommercial coalescent aid, TEXANOL® (Eastman Kodak). Both of high Tglatex polymers used in this invention provided good blocking resistance.

PENCIL HARDNESS TEST RESULTS Semigloss paint Hardness rating AcronalA846 + TEXANOL ® 2B Acronal A846 + Methyl Ester 2B Acronal A846 +EG-derivative 3B Ucar 430 + TEXANOL ® 4B Ucar 430 + Methyl Ester 4B Ucar430 + EG-derivative 5B

Hardness of film from paint formulation with ethylene glycol soy oilester as a coalescent aid was lower than hardness of film from paintformulation with the commercial coalescent aid, TEXANOL® (EastmanKodak). Both of high Tg latex polymers used in this invention providedless hardness.

ADHESION TEST Surface of cross-cut area from which flaking has occurredSemigloss high Tg latex (with epoxy primer) Acronal A846 +TEXANOL ® >65% Acronal A846 + Methyl Ester >65% Acronal A846 +EG-derivative >65% Ucar 430 + TEXANOL ® >65% Ucar 430 + MethylEster >65% Ucar 430 + EG-derivative >65%

Paint formulation with both high Tg latex polymers and ethylene glycolsoy oil ester as a coalescent aid, exhibited poor performance inadhesion of paint film on epoxy-primed aluminum panel. The same poorperformance occurred with the commercial coalescent aid, TEXANOL®(Eastman Kodak).

Example 5

Evaporation rate of new glycol derivative soy oil ester relatively toconventional coalescent aids, TEXANOL® (Eastman Kodak) and Ethyleneglycol n-Butyl ether (Union Carbide).

Weighed three replicas of each coalescent aid into aluminum pans. Keepall aluminum pans with coalescent at room temperature. The percentage ofweight loss of each coalescent aid was measured.

The evaporation rate of ethylene glycol, propylene glycol and methylester derivatives as well as TEXANOL® (Eastman Kodak) and Ethyleneglycol n-Butyl ether (EB, Union Carbide) are shown below in FIG. 5.

The evaporation rates of glycol derivative and methyl soy oil ester arelower than comparative coalescent aids (TEXANOL® and EB). Ethyleneglycol monobutyl ether is water-soluble coalescent aid and evaporatefrom the film and is therefore a VOC. TEXANOL®, water-insolublecoalescent aid could gradually evaporate from the film while it isaging. The new soy oil glycol ester in this invention does not show aloss in weight. This means new soy oil glycol ester would become a partof coating film, and does not give off VOCs. The data indicates a slightbut real increase in weight after 2 days consistent with a drying oilreacting slowly with air to cure.

MFFT Measurement with the Incorporation of Glycol Palmitate, Oleate andLinoleate.

Ethylene glycol derivatives of palmitic acid, oleic acid and linoleicacid were added to coatings formulated with high Tg resin (Ucar 430 andAcronal A846) at levels of 0.5%, 0.75% and 1.0% by weight. Theformulations were equilibrated for two days before taking MFFTmeasurement.

The MFFT results are shown in FIGS. 6-9.

UCAR 430

The results from the MFFT measurements of high Tg resin (UCAR 430,PS/PMMA) formulation are shown in FIGS. 6 and 7. As FIGS. 6 and 7illustrate, it was found that glycol fatty acid ester and glycol soy oilester could lower the minimum film formation temperature better thanethylene glycol monobutyl ether (EB). This may be due to the slowevaporation rates of the glycol fatty acid ester and glycol soy oilester relative to ethylene glycol monobutyl ether. Thus the coalescentnew aids may stay in the system long enough to function in lowering theminimum film formation temperature. As shown in FIG. 7, all glycol soyoil esters could reduce the minimum film formation temperature in thesame fashion as commercial coalescent aid, TEXANOL®.

Some of glycol fatty acid esters, i.e. methyl soyate, ethylene glycololeate and ethylene glycol linoleate, could lower the minimum filmformation temperature better than TEXANOL®. Methyl soyate ester couldlower the MFFT the best.

ACRONAL A846

The MFFT results of high Tg resin (ACRONAL A846, pure acrylic resin)formulation, it was found that all glycol fatty acid ester and glycolsoy oil esters could lower the minimum film formation temperature betterthan ethylene glycol monobutyl ether (EB). They also could reduce theminimum film formation temperature in the same manner as commercialcoalescent aid, TEXANOL®. None of them could lower the minimum filmformation temperature better than TEXANOL® except ethylene glycol soyoil ester at concentration of 1.0% by weight.

Example 6

AC Impedence measurements were taken to obtain the trend of the coatingcapacitance and coating resistance values as a function of dry time toexpress the film formation of latex coating as a function of dry time.In addition, the measurements with various coalescent aid formulationswould also impact the effect of coalescent aid in latex film formation.

AC Impedence measurements were taken on 0.5% EB as a function of drytime, 0.5% TEXANOL® as a function of dry time, and 0.5% ethylene glycolsoy oil ester as a function of dry time. A two-time constant equivalentcircuit model, as a hypothetical equivalent circuit for the coatedaluminum system, was used to correlate the Bolt and Nyquist result plotsfrom the AC Impedence measurements. The coating resistance, coatingcapacitance, charge transfer resistance, and associated double layercapacitance obtained were plotted as a function of dry time. As FIG. 10illustrates, the coating resistance increased as a function of dry timeuntil approximately 8 hours dry time, then it leveled off. For thecharge transfer resistance, there was a slight increase in theresistance which was not significant. This was because there was nocorrosion taking place.

The coating capacitance plot (shown in FIG. 11) exhibited a decreasingtrend as a function of dry time until approximately 8 hours then thecapacitance was constant. This trend can be explained by the phenomenonthat at shorter drying periods, the coating film was not completelycoalesced, and there remained pores and the diffusion of electrolytesolution through the film could take place which resulted in theincrease in film capacitance. For the longer drying periods the film wasmore coalesced and less diffusion took place. Therefore, the resistanceof film is higher and the capacitance was lower as a function of longerdry periods.

As FIGS. 10 and 11 illustrate, the AC Impedance measurements showed anincrease in coating resistance and a decrease in coating capacitance aswell as the formulation with the conventional coalescent aid, TEXANOL®.This supported the contention that soybean oil coalescent aid effectedlatex film formation as well as TEXANOL®.

Example 7

Various IR and NMR spectra were taken of glycol soybean oil esterderivatives, methyl soybean oil derivatives, and ethylene glycol fattyacid derivatives.

IR-Spectra

Infrared spectra of soybean oil and soybean oil ester derivatives areshown in FIGS. 12-19. FIG. 12 shows the IR spectrum of soybean oil.FIGS. 13-17 show the IR spectra of the soybean oil ester derivatives ofethylene glycol (FIG. 13), propylene glycol (FIG. 14), diethylene glycol(FIG. 15), dipropylene glycol (FIG. 16) and the methyl soybean oil esterderivative (FIG. 17). FIG. 18 shows the IR spectrum of the ethyleneglycol oleate ester derivative and FIG. 19 shows the IR spectrum of theethylene glycol linoleate ester derivative.

¹H-NMR DATA

¹H-NMR spectra were obtained for soybean oil and soybean oil esterderivatives. FIG. 20 shows the ¹H-NMR spectrum of soybean oil. FIGS.21-25 show the ¹H-NMR spectra of the soybean oil ester derivatives ofethylene glycol (FIG. 21), propylene glycol (FIG. 22), diethylene glycol(FIG. 23), dipropylene glycol (FIG. 24) and the methyl soybean oil esterderivative (FIG. 25). The ¹H-NMR spectrum of the ethylene glycol oleateester derivative is shown in FIG. 26, and FIG. 27 shows the ¹H-NMRspectrum of the ethylene glycol linoleate ester derivative.

¹³C-NMR DATA

¹³C-NMR DATA spectra were obtained for soybean oil and soybean oil esterderivatives. FIG. 28 shows the ¹³C-NMR DATA spectrum of soybean oil.FIGS. 29-32 show the ¹³C-NMR DATA spectra of the soybean oil esterderivatives of ethylene glycol (FIG. 29), propylene glycol (FIG. 30),diethylene glycol (FIG. 31), and dipropylene glycol (FIG. 32).

Example 8

Physical properties such as solubility parameters, HydrophilicLipophilic Balance values (HLB values), density, and surface tensionwere measured of various soybean oil esters, ethylene glycol monobutylether (EB), and TEXANOL®. The soybean oil esters included ethyleneglycol soybean oil derivative, diethylene glycol soybean oil derivative,propylene glycol soybean oil derivative, dipropylene glycol soybean oilderivative, and methyl ester soybean oil derivative.

Soy oil derivative esters EG^(a) DEG^(b) PG^(c) DPG^(d) ME^(e) EB^(f)TEXANOL ®^(g) Properties Density 0.94 0.93 0.91 0.91 0.87 (g/cm³) HLB2.7 4.8 3.4 5.9 N/A 14.9 N/A Interfacial 36.2 36.1 33.3 35.7 30.1 27.428.9 tension (dyne/cm) Solubility Parameters _(δtotal) (J/ 18.6 18.218.0 17.6 17.9 20.7 19.3 cm³)^(1/2) _(δd)(J/ 16.2 15.8 15.7 15.4 17.215.9 15.6 cm³)^(1/2) _(δp)(J/ 2.03 2.04 1.88 1.85 1.50 4.9 3.07cm³)^(1/2) _(δh)(J/ 8.8 8.7 8.5 8.3 4.6 12.3 10.9 cm³)^(1/2)^(a)Ethylene glycol soybean oil derivative (EG) ^(b)Diethylene glycolsoybean oil derivative (DEG) ^(c)Propylene glycol soybean oil derivative(PG) ^(d)Dipropylene glycol soybean oil derivative (DPG) ^(e)Methylester soybean oil derivative (ME) ^(f)Ethylene glycol monobutyl ether(EB) ^(g)TEXANOL ®

From the solubility parameters shown in the table above, it was foundthat the total solubility parameter of EB is greater than TEXANOL® andthe glycol soybean oil derivatives. In addition, the polar solubilityparameter (*_(p)) and hydrogen bonding solubility parameter (*_(h))decreased in the order of EB>TEXANOL®>glycol soybean oil derivatives.Therefore, EB would be able to be miscible with water better thanTEXANOL® and glycol soybean oil derivatives.

The solubility parameter of a polymer, the polystyrene methylmethacrylate copolymer (PS-MMA, UCAR 430) was considered. The solubilityparameter of PS-MMA is 18.2 (J/cm3)½ as stated in J. Brandrup and E. H.Immergut, Polymer Handbook, 2^(nd) ed., Wiley-Interscience, New York, p519 (1989). It was found that the solubility parameter of glycol soy oilesters and TEXANOL® were close to that of polystyrene rather than EB.Ideally for hydrophobic coalescent aids, a solubility parameter matchwill produce a better coalescent aid. As a result, TEXANOL® and glycolsoybean oil derivatives should coalesce the polystyrene methylmethacrylate copolymer (UCAR 430) better than EB.

Higher HLB values correspond with greater miscibility with water. In theabove table the HLB value of EB was greater than that of glycol soybeanoil derivatives. This corresponded with the solubility parameter of EB.Therefore, EB would be miscible with water better than glycol soybeanoil derivatives.

The value of the interfacial tension is a measure of the dissimilarityof the two types of molecules facing each other across the interface.The smaller the interfacial tension, the more similar in nature the twomolecules are, and the greater the interaction between the molecules. Inthe table above the interfacial tension of EB was 27.4 dyne/cm which wasless than those of TEXANOL® and glycol soybean oil esters. Therefore, EBwould be miscible with water better than TEXANOL® and glycol soybean oilesters.

1. A film-forming composition comprising a continuous aqueous phase anda dispersed phase, the dispersed phase comprising (i) an emulsifiedliquid prepolymer, and (ii) a coalescent aid comprising an esterselected from the group consisting of the methyl, ethylene glycol,diethylene glycol, propylene glycol, and dipropylene glycol esters of afatty acid of corn oil, sunflower oil, soybean oil, or linseed oilwherein the weight of the ester is (i) about 0.1% to about 4% of theweight of the liquid prepolymer and (ii) at least about 50% of thecoalescent aid.
 2. The film-forming composition of claim 1 wherein thecoalescent aid comprises an ester selected from the group consisting ofthe ethylene glycol, diethylene glycol, propylene glycol, anddipropylene glycol esters of a fatty acid of corn oil, sunflower oil,soybean oil, or linseed oil.
 3. The film-forming composition of claim 1wherein the coalescent aid comprises an ester selected from the groupconsisting of the ethylene glycol, diethylene glycol, propylene glycol,and dipropylene glycol esters of a fatty acid of sunflower oil.
 4. Thefilm-forming composition of claim 1 wherein the coalescent aid comprisesan ester selected from the group consisting of the ethylene glycol,diethylene glycol, propylene glycol, and dipropylene glycol esters of afatty acid of soybean oil.
 5. The film-forming composition of claim 1wherein the coalescent aid comprises an ester selected from the groupconsisting of the ethylene glycol, diethylene glycol, propylene glycol,and dipropylene glycol esters of a fatty acid of linseed oil.
 6. Thefilm-forming composition of claim 1 wherein the coalescent aid comprisesthe methyl ester of a fatty acid of corn oil, sunflower oil, soybeanoil, or linseed oil.
 7. The film-forming composition of claim 1 whereinthe weight of the ester is about 1% to about 4% of the weight of theliquid prepolymer.
 8. The film-forming composition of claim 1 whereinthe ester is an ethylene glycol monoester derived from a fatty acid ofsoybean oil.
 9. The film-forming composition of claim 1 wherein theester is an ethylene glycol monoester of a fatty acid derived fromsunflower oil.
 10. The film-forming composition of claim 1 wherein theester is a diethylene glycol monoester of a fatty acid derived fromsoybean oil.
 11. The film-forming composition of claim 1 wherein theester is a diethylene glycol monoester of a fatty acid derived fromsunflower oil.
 12. The film-forming composition of claim 1 wherein theester is a methyl ester of a fatty acid derived from soybean oil. 13.The film-forming composition of claim 1 wherein the ester is a methylester of a fatty acid derived from sunflower oil.
 14. The film-formingcomposition of claim 1 wherein the ester is an ethylene glycol monoesterof a fatty acid derived from corn oil.
 15. The film-forming compositionof claim 1 wherein the ester is an ethylene glycol monoester of a fattyacid derived from linseed oil.
 16. The film-forming composition of claim1 wherein the continuous aqueous phase constitutes at least about 20 wt.% of the film-forming composition.
 17. The film-forming composition ofclaim 1 wherein the dispersed or continuous aqueous phase furthercomprises an additive selected from the group consisting of wettingaids, dispersants, thickeners, defoaming agents, biocides, algicides,ultra-violet inhibitors, flow agents, levelling agents, rheologymodifiers, freeze thaw stabilizing agents, pH modifiers, flash rustinhibitors, and biocides.
 18. The film-forming composition of claim 1wherein the film-forming composition contains at least about 20 wt. %water, and at least about 10 wt. % liquid pre-polymer.
 19. Thefilm-forming composition of claim 1 wherein the continuous aqueous phasecontains less than about 10 wt. % organic solvent.